Insights into the Synergistic Catalytic Effect of TiO2 Supported V‐W Oxides for Selective C−H Bond Oxidation of Cyclohexane to KA Oil

It is urgent to develop an efficient and stable non‐noble metal catalyst for selective C−H bond oxidation of cyclohexane. Herein, a series of V−W oxides supported on TiO2 catalysts (V−W/TiO2) were fabricated. The V−W/TiO2 catalysts exhibited much higher catalytic activity for the selective oxidation of cyclohexane to KA oil, compared to that of V/TiO2 and W/TiO2 catalysts. The good distribution of active metals and the synergistic effect were responsible for the enhanced catalytic activity. H2‐TPR results disclosed that the presence of V in V−W/TiO2 affected the reducibility of W6+ species, and XPS verified that an electronic interaction was formed between them. Such results led to good catalytic reusability of V−W/TiO2 catalyst during the reactions, and no obvious activity loss was found after six runs. The reaction mechanism was investigated, and the results verified that hydroxyl radicals generated from H2O2 homolysis were the main active oxidative species. Theoretical study revealed that V dopant could regulate electronic structure of adjacent O atom, facilitating the adsorption of cyclohexane, and lower energy was needed for the rate‐limiting step over V−W/TiO2 during the whole oxidation reaction. This work developed an efficient V−W/TiO2 catalyst for the selective oxidation of cyclohexane via a synergistic effect. The TiO2 supported V−W bimetallic oxides catalyst was prepared and used for the catalytic oxidation of cyclohexane to KA oil with H2O2 as an oxidant, and the prepared catalyst exhibited satisfactory catalytic activity owing to the synergistic effect between V and W.